Reaction mixture derived from oleic acid, sebacic acid, and triethylene tetramine



3,050,527 Patented Aug. 21, 1962 United States Patent ()fiice Immediately after adding all of the triethylene tetramine, the system is protected during synthesis against catalytic pro-oxidant metals by the addition of a chelating and inactivating agent. These metals, which are introduced as impurities in the acid and amine reactants,

Brookline, Mass, assignors to W. R. Grace 8; C0., catalyze degradation of the reaction product with a con- Cambridge, Mass, a corporation of Connecticut sequent increase in viscosity and darkening of the prod- NO Drawing- Filed N 73,351 not. Even small leaks in the packing surrounding the 3 zli-swfl) agitator shaft through which atmospheric oxygen can This invention relates to compositions containing a 10 gain entrftmce l h mixing vessel P a tenfold complex compound having a plurality of imidazoline mcre'flse the V1ScOS 1ty- The agent added In amounls rings as a principal constituent In another aspect it suflicient to react with substantially all of the metallic relates to a method for preparing such Compositions by impurities present in the reactants and generally between contacting a plurality of diverse carboxylic acids and a about 1 Percent to percent, by Welght based on h polyethylene polyamin u d reactive conditions 15 total weight of the acids and amine has been found satis- Monoimidazolines, such as undecylimidazoline, and di- Iactory Sultable agents Include the alkah metal Poly imidazolines, such as octamethylene diimidazolinc, are ggg s Such as Sodlum and potassium tripolyphos known but have limited utility. The complex polyimidazoline of this invention has a high molecular weight, i mlxture, 1S thiin hcated at 1 atmosphere to about is strongly basic, and possesses strong surface activity. 9 at f' f l t pressurefmd temperature are when incorporated with a polymeric mammal, Such as admsted periodically in inverse relationship according to polymers and copolymers of vinyl chloride, it performs the followmg Schedule: admirably as a curing agent.

The present compositions are prepared by heating 3,050,527 REACTION MIXTURE DERIVED FRGM OLEIC ACID, SEIBACIC ACID, AND 'I'RHETHYLENE TETRAMINE Elizabeth C. Dearborn, Boston, and Philip K. Isaacs,

olelc and Sebaclc acids a tnethyienfi stramme at.re 20 Heating period inminutes alter Temperature Pressure duced pressures under nitrogen while vigorously agitatreaction mixture has reached 150 0. O 0, mm ing the reactants. imidazoline formation proceeds essentiaily in two steps. In the first step a terminal amino group of the polyamine reacts with a carboxyl group to 232 form an amide with the release of one mole of water. 155 335 Then, a second mole of water splits out from the amide 1 2 group and a secondary amino group beta to it, causing 1915 110 cyclization to give an imidazoline. Dicarboxylic acids reacting with polyamines in this manner produce a com- 220 15 plex polyimidazoline containing imidazoline rings plus some amide groups and secondary amino groups resulting from incomplete cyclization.

Th ti yields a i t comprising a major Since water catalyzes side reactions and hydrolyzes imidamount of (1) a polyimidazoline havi th f n i azoline, it is removed as it is formed in order to achieve idealized structure maximum conversion to imidazoline. The above sched- O11H33C-NCH2CHz-N-CCsHirC-NOHz-CHz-NCCi1Haa IQT 6H2 Ha I l N CH: 1120 N CfiZ Chi OH; OH;

in which up to about 20 percent of the original carboxyl 1116 Permits removal of Water as fast as possible congroups are in the form of unconverted amides sistent with imidazoline conversion without distilling appreciable amounts of tetramine. During the reaction I] I period, the agitator should be run at a high rate of speed TC N OH2 CH2 to give a high surface turnover of the mixture for rapid derived from the reaction of acid with primary amine water removal. An agitator speed of about 100-200 groups, and/or N-substituted amides r.p.m. has been found to be satisfactory. Experiments have shown that low water removal caused by decreasing the speed from about 150 to 65 rpm. lowered the imid- 5 azoline content by about 10 percent due to irreversible hydrolysis of the imidazoline ring.

After a temperature of about 220 C. and a pressure derived from either hydrolysis of previously formed imidazoline rings or the reaction of acid with secondary amine p and/01 Species of imdaZOlineS and of about 15 mm. Hg have been reached within three hours Polyimidazolines having higher and lower 111016011131 according to the foregoing schedule, this pressure and weights than the molecular weight of the idealized polytemperature are held and the reaction mixture is heated imidazoline structure. for about one hour under these conditions. Thereafter In carrying out the invention, the oleic acid is first the product is cooled to 150 C. under nitrogen and charged to a g ss miXing s l and t n the SebaCiC collected. The viscosity of the reaction product averages acid is stirred in. Agitation is continued throughout the about 1,200 centipoises at 60 C. The average composireaction period. The acid mixture is deoxygenated at a tion as determined by infrared absorption is comprised pressure of about 15 mm. Hg, the vacuum is released of structures resulting from about percent conversion with nitrogen and a blanl-(eting stream of nitrogen is thereof the carboxyl groups to imidazoline rings with the reafter used throughout the reaction. Following deoxymaining 20 percent of the original carboxyl groups being genation, the acids are heated to about 70 C., the converted to amide groups. requisite amount of triethylene tetra-mine is added and 70 The molar quantities of acids and amine used to prethe temperature rises to about C. due to salt formapare the reaction mixture are 2 moles of oleic acid, 1 tion. mole of sebacic acid and 2 moles of triethylene tetramine.

"3 C9 The invention is further illustrated by the following examples:

Example 1 339 lbs. (1.2 moles) of oleic acid were charged to a glass vacuum vessel and then 121 lbs. (0.6 mole) of sebacic acid were added. The acids were heated to about 70 C. and then 175 lbs. (1.2 moles) of triethylene tetramine were added. Due to the exothermic nature of the reaction between the amine and acids, the temperature of the mixture rose to about 100 C. 0.64 lb. of powdered sodium tripolyphosphate was then added as a metal chelating agent. Vigorous agitation and a nitrogen atmosphere were maintained throughout. The mixture was then heated at 1 atmosphere to about 150 C. and the temperature and pressure were carefully controlled there after for a four-hour period according to the pressuretemperature schedule set forth hereinbefore. During this period, water of condensation was continuously removed to avoid hydrolysis of the imidazolines. The amount of water removed over the entire reaction period corresponded with about 80 percent conversion of the carboxyl groups to imidazoline groups, leaving a balance of about 20 percent of the carboxyl groups in the form of amides. The composition of the reaction mixture was confirmed by infrared absorption analysis. Finally, the product was cooled under a nitrogen to about 130 C.

The utility of the reaction product is demonstrated in the following Example 2:

Example 2 3 percent vinyl acetate), 20 parts of Flexol EP-8 (epoxidized 2-ethylhexyl ester of tall oil acids), and 5 parts of zinc oxide. This formulation was cured at 200 C. for 4, 8, and 12-minutes periods. The properties of the cured product were as follows:

These properties suggest a use for the cured product where color, flexibility and adhesion, taken independently or collectively, are prime criteria.

We claim:

1. A composition derived by reacting in a dcoxygenated system 2 moles of oleic, 1 mole of sebacic acid and 2 moles of triethylene tetramine at a temperature of about 50 C. to 240 C. and a pressure of about 10 to 760 mm. Hg while continuously removing the water of reaction, and continuing the reaction until the fiow of water of reaction substantially ceases.

2. A composition according to claim 1 wherein the reaction is carried out in the presence of a small amount of a chelating agent.

3. A composition according to claim 2 wherein the chelating agent is sodium tripolyphosphate.

References Cited in the file of this patent UNITED STATES PATENTS 2,374,354 Kaplan Apr. 24, 1945 2,568,876 White et a1 Sept. 25, 1951 2,668,165 Carpenter Feb. 2, 1954 2,846,440 Hughes Aug. 5, 1958 2,917,376 Stromberg et al Dec. 15, 1959 

1. A COMPOSITIONS DERIVED BY RACTING IN A HYDROGENATED SYSTEM 2 MOLES OF OLEIC, 1 MOLE OF SEBACIC ACID AND 2 MOLES OF TRIETHYLENE TETRAMINE AT A TEMPERATURE OF ABOUT 50*C. TO 240*C. AND A PRESSURE OF ABOUT 10 TO 760 MM. HG WHILE CONTINUOUSLY REMOVING THE WATER OF REACTION, AND CONTINUING THE RACTION UNTIL THE FLOW OF WATER OF REACTION SUBSTANTIALLY CEASES. 